Polyoxyalkylene derivatives of phenothiazine



atent 2,815,343 Patented Dec. 3, 1957 fine POLYOXYALKYLENE DERIVATIVESOF PlENOTl-HAZINE Lee H. Horsley and Harold 0. Seeburger, Midland,Mich., assignors to The Dow Chemical Company, Midland, Mich., acorporation of Delaware No Drawing. Application December 10, 1956,Serial No. 627,130

14 Claims. (Cl. 260-243) This application is a continuation-in-part ofour copending applications Serial Numbers 472,759 and 472,760 both filedDecember 2, 1954, both now abandoned.

This invention relates to polyoxyalkylene derivatives of phenothiazineand phenothiazine-S-oxide.

The compounds of the invention are N-substituted polyoxyalkylenederivatives of phenothiazine and phenothiazine-S-oxide in which thepolyoxyalkylene chain is composed of oxyalkylene units formed from oneor more vicinal alkylene oxides, i. e. those alkylene oxides in whichthe oxygen atom is bonded to each of two contiguous carbon atoms. Thesenovel compounds correspond to the general formula:

wherein m is an integer from to 1, -(RO),, is a polyoxyalkylene chainwherein R is the bivalent hydrocarbon residue from a member of the groupof alkylene oxides consisting of ethylene oxide, propylene oxide, 1,2-and 2,3-butylene oxides, styrene oxide and mixtures thereof, and n is anumber in the range of 2 to 100.

The compounds are made by condensing a plurality of moles of one or morealkylene oxides with a mole of phenothiazine or phenothiazine-S-oxide,condensation occurring on the nitrogen atom of the phenothiazinenucleus. When more than one alkylene oxide is used, the oxides may beadded in mixture to form a chain of randomly mixed oxyalkylene units, orthey may be added separately in sequence to form a composite chainconsisting of sequential groups of polyoxyalkylene units arranged in anorder according to the order of addition of the respective alkyleneoxides. Alkylene oxides that may be used according to the invention areethylene oxide, propylene oxide, 1,2- and 2,3-butylene oxides, styreneoxide, and mixtures of any of them. A given product may be composed of amixture of compounds having varying chain lengths, the average of whichapproximates the number of moles of oxide that are added during thereaction. Within the scope of the invention, the chain length may varyfrom 2 to 100 or more oxyalkylene units. In general, those productshaving an average of from 5 to 50 oxyalkylene units in thepolyoxyalkylene chains are preferred.

The new compounds are usually prepared by reacting two or more moles ofalkylene oxide with one mole of phenothiazine or phenothiazine-S-oxide.Alternatively, a polyoxyalkylene glycol may be reacted withphenothiazine or the S-oxide.

The alkylene oxide condensation with phenothiazine or its 5-oxide iscarried out under substantially moisturefree conditions at an elevatedtemperature inthe presence of any of the usual condensation catalysts,an alkali metal hydroxide or alkoxide being preferred. The amount ofcatalyst employed should be at least 0.1 percent, preferably from 1 to 5percent, by weight of the quantity of phenothiazine compound used, orfrom 0.1 to 1 percent by weight based on the total reactants. Reactiontemperatures are in the range of about to 200 C., with temperaturesabove C. but below C. preferred during most of the reaction.Superatmospheric pressures are ordinarily required, e. g. from 10 to 200pounds per square inch, gauge. Atmospheric pressure may be used,however, when reacting an alkylene oxide, such as styrene oxide, whichis' normally liquid at the reaction temperature.

Since phenothiazine and its 5-oxide are solids melting at about 185 and256 C., respectively, they may be dissolved in an inert diluent, such asbenzene, toluene, or xylene, which is a common solvent both for thereactants and the reaction products. Alternatively they may be liquefiedat a temperature substantially below 180 and 200 C., respectively bydissolving them in a small amount of the alkylene oxide. Once thereaction gets under way, they will remain dissolved in the reactionmixture.

A preferred method of conducting the reaction is to add the alkyleneoxide, or mixed oxides, gradually to the hot liquefied phenothiazinecompound, or solution thereof, and catalyst, while maintaining the wholeat a reaction temperature and under sufiicient pressure to maintain theliquid state. The alkylene oxide may be continuously added to thereaction vessel at a fairly rapid rate, as fast as it is reacted. Bycontinuous rather than intermittent addition of alkylene oxide, thecontrol of the reaction is simplified. The alkylene oxide should besubstantially anhydrous, e. g. the moisture content of the oxideordinarily should not exceed about 0.1 percent by weight. The alkyleneoxide should also be as free as practical from contaminants, such asaldehydes, which give rise to side reactions and by-product formation.

The reaction is exothermic. It is therefore necessary to remove the heatof reaction by provision of adequate cooling means. When pressure isemployed, it is desirable to maintain it fairly constant at somepredetermined value by controlling the rate of addition of the alkyleneoxide.

After all of the alkylene oxide, or mixture of oxides, have been addedto the reaction vessel, the contents are maintained at a reactiontemperature for a time sufiicient to complete the reaction. Uponcompletion of the reaction, the mixture may be cooled, removed, andworked up to separate the product. In working up the reaction product,it is first neutralized, e. g. with carbon dioxide, to inactivate thealkaline catalyst, and then heated at a reduced pressure under reflux todistill off any low-boiling material, mainly unreacted alkylene oxide.Following topping under vacuum, the product, while still warm, may befiltered, if necessary, to clarify it.

The reaction may also be carried out in a continuous manner bycontinuously feeding the reactants into a reaction chamber underconditions of good mixing, while maintaining a reaction temperature andsufliciently long residence time to complete the reaction.

The compounds of the invention are liquids or solids, depending upon thelength and composition of the polyoxyalkylene chains attached to thephenothiazine nuclei. They have good thermal stability, low vaporpressures, high flash points, good lubricating properties, and aremiscible with a variety of solvents. In addition, they are stable inair, do not deposit gummy residues on heating, and are non-corrosive tometals. The compounds based largely or solely on ethylene oxide areliquid or soft, waxy solids, depending on their molecular weight. Theyare water soluble and have powerful surfactant properties,

EXAMPLE 1 A 500 milliliter, electrically heated, stainless steel,rocking-type autoclave equipped with a thermocouple, pressure gauge, andinlet tube was charged with 59.7 grams (0.30 mole) of phenothiazine, 150grams of toluene, and 1.0 gram of solid sodium hydroxide. The autoclaveso charge-d was then cooled to about C., flushed With dry nitrogen gas,and additionally charged with 26.4 grams (0.60 mole) of liquid ethyleneoxide. Thereupon the autoclave was closed, set to rocking, and heated toabout 100 C. at which temperature the pressure rose to 49 pounds persquare inch, gauge. thereafter, as reaction took place, the temperaturerose to and was maintained at, about 150 C., the pressure falling off to35 p. s. i. g. as the reaction progressed. After a reaction time of 45minutes, the reaction mixture was quenched by cooling the autoclave andits contents to about 20 C. The crude reaction product Weighing 230grams was filtered and 16 grams of insoluble solid phenothiazine wasremoved. The filtrate was then neutralized with carbon dioxide and latersubjected to distillation under reduced pressure to remove toluene. Theresidue, weighing 67 grams, was a viscous, amber-colored, waterinsolubleoil, being a mixture of N-polyoxyethylene derivatives of p'henothiazinehaving an average molecular weight of approximately 288 as calculatedfrom the hydroxyl value, the oxyethylene chains attached to thephenothiazine nuclei therefore containing an average of approximately 2oxyethylene units.

EXAMPLE 2 1n the 500 milliliter steel autoclave of Example 1 werereacted 52.8 grams (1.20 moles) of ethylene oxide and 29.9 grams (0.15mole) of phenothiazine dissolved in 150 grams of toluene, to which 0.5gram of solid sodium hydroxide was added. The reaction was carried outaccording to the procedure of the preceding example at a temperature ofabout 120 C., a maximum pressure of 105 p. s. i. g. being observed. Whenthe reaction had gone substantially to completion, the reaction productwas cooled, neutralized, and topped to remove toluene by distillationunder reduced pressure. The residue, weighing 82 grams, was a viscousoil of limited water solubility, being a mixture of N-polyoxyethylenederivatives of phenothiazine having an average molecular weight ofapproximately 530. The polyoxyethylene chains attached to thephenothiazine nuclei contained an average of approximately 8 oxyethyleneunits.

The above-described product was tested for fungicidal activity byspraying it in aqueous solution onto the leaves of various vegetableplants and subsequently inoculating the plants with spores ofdisease-producing fungi. At concentrations as low as 1 pound per 100gallon of water, this product was found to be effective in controllingfungus diseases such as bean mildew and tomato early blight.

EXAMPLE 3 A 2-liter stainless steel autoclave equipped with athermocouple, pressure gauge, and inlet tube was charged with 199 grams(1.0 mole) of phenothiazine and 3 grams of solid potassium hydroxide.The autoclave was then flushed with dry nitrogen gas, cooled to belowC.,

Shortly all) and sealed. Approximately 165 grams of liquid ethyleneoxide was then introduced into the autoclave, which was placed in anelectrically heated steel rocker, set to rocking, and heated slowly toabout C. At this temperature, the reaction began at a fast rate and thepressure rapidly dropped from a peak of about 200 pounds per square inchgauge. Thereafter the temperature was maintained at about 150 C. forapproximately 1 hour until the reaction was substantially complete, i.e. until the gauge pressure had fallen off to about 0 p. s. i. Theautoclave was then again cooled, evacuated of its gaseous atmosphere,and recharged with 363 grams of liquid ethylene oxide, thus bringing thetotal weight of ethylene oxide charged up to 528 grams (12.0 moles). Thecontents of the autoclave was then reacted to completion in accordancewith the above described procedure, whereupon the autoclave was cooledand the liquid reaction product transferred to a flask. This product wasneutralized with carbon dioxide, heated to 150 C. at a pressure of 20millimeters of mercury absolute to remove low boiling material, andfiltered while still hot. The final product was a mixture ofN-polyoxyethylene derivatives of phenothiazine having an average ofabout 12 oxyethylene units in the polyoxyethylene chain attached to thephenothiazine nucleus. It was a viscous, amber-colored, liquid, having awater solubility at 25 C. of greater than 50 weight percent. A 10percent solution by weight of this product had a cloud point of about 70C., i. e. above this temperature the product was no longer soluble inwater to the extent of 10 percent. This product is similar to theproduct of Example 2 in fungicidal activity.

EXAMPLE 4 A mixture of N-polyoxyethylene derivatives of phenothiazinehaving an average of about 16 oxyet'hylene units in the polyoxyethylenechain attached to the phenothiazine nucleus was prepared by reacting atotal of 704 grams (16.0 moles) of ethylene oxide and 199 grams (1.0mole) of phenothiazine at a temperature of about C. according to theprocedure of Example 3. The reaction product was a straw-colored,water-soluble soft wax having a cloud point of approximately 85 C. Thewater solubility of this product was greater than 50 Weight percent at25 C. This product is an elfective fungicide, being similar in thisrespect to the products of Examples 2 and 3.

EXAMPLE 5 The autoclave employed in Example 3 was charged with 199 grams(1.0 mole) of phenothiazine, 232 grams (4.0 moles) of 1,2-propyleneoxide, and 3 grams of solid potassium hydroxide. The contents were thenheated at a temperature of about 150 C. in accordance with the procedureof Example 3. There was obtained a phenothiazine-polyoxypropylenereaction product having an average of about 4 oxypropylene units in eachpolyoxypropylene chain. This reaction product was then heated at aboutC. with 528 grams (12.0 moles) of ethylene oxide, thereby formingpolyoxyethylene extensions of the polyoxypropylene chains. The finalproduct was a viscous amber liquid, having a water solubility of greaterthan 50 weight percent at 25 C. and a cloud point of approximately 65 C.in 10 Weight percent Water solution.

This product was tested as a detergent by standard launderometer testsand found to be as good or better than several well-known commercialdetergents of the anionic type, e. g. sodium alkylarylsulfonatescontaining builders.

The product of Example 5 was also tested as an antioxidant forlubricating oils, e. g. low viscosity index turbine oil, and found to besuperior in this respect to phenothiazine itself.

EXAMPLE 6 A total of 435 grams (7.5 moles) of 1,2-propylene oxide wasreacted with 298.5 grams (1.5 moles) of phenothiazine at an averagetemperature of about 150 C. in the presence of 3.0 grams of KOH catalystaccording to the procedure of Example 3. Based on the total charge, thisrepresents a reactant ratio of moles of 1,2- propylene oxide per mole ofphenothiazine and a theoretical molecular weight of 489 for the product.After neutralizing the product with carbon dioxide and removing the lowboilers by distillation at reduced pressure, the hydroxyl value of theproduct was determined with phthalic anhydride and an average molecularweight of 431 was calculated therefrom.

Other properties were also determined for the product, viz., therefractive index, specific gravity, cloud point, and solubilities invarious solvents. These data are shown in Table I. As therein given, thecloud point is the temperature in degrees centigrade at which a weightpercent water solution of the product became cloudy and the solubilitiesare qualitative determinations of the solubility of the product in anequal part by weight of each of several named solvents at 25 C., thesame being expressed as soluble (S), slightly soluble (SS), or insoluble(IS).

In addition, the product of this example was tested and found to be veryefiective as an aphicide at a concentration of only 0.35 weight percent.This product, similar to that of Example 5, was also found to be a goodantioxidant for petroleum oils.

EXAMPLE 7 Propylene oxide Weighing 580 grams (10.0 moles) was reactedwith 199 grams (1.0 mole) of phenothiazine at an average temperature of150 C. in the presence of 3 grams of KOH as catalyst and according tothe procedure employed in the preceding example. The product was a darkbrown viscous liquid having an average molecular weight of 610 ascalculated from the hydroxyl value. This and other product data areshown in Table I.

The product of this example was also found to be a good antioxidant forlubricating oils.

EXAMPLE 8 A mixture of 504 grams (7.0 moles) of 1,2- and 2,3- butyleneoxides in a weight ratio of about 9 to 1 was reacted with 278.6 grams(1.4 moles) of phenothiazine at an average temperature of about 150 C.employing 3 grams of KOH as catalyst in accordance with the generalprocedure of Example 3. This represents a butylene oxide tophenothiazine molar ratio of 5 to l. The product was a light brownviscous liquid having an average molecular weight of 461 as calculatedfrom the hydroxyl value. Physical data are shown in Table I.

EXAMPLE 9 A total of 440 grams (10.0 moles) of ethylene oxide and 79.6grams (0.4 mole) of phenothiazine was reacted at an average temperatureof about 150 C. in the presence of 2 grams of KOH catalyst according tothe general procedure of Example 3. This represents a molar reactantratio of 25 moles of ethylene oxide to 1 mole of phenothiazine. Thisproduct was a brown waxy solid having a melting point of about 33.5 C.and an average molecular weight of 1055 as calculated from the hydroxylvalue. For additional physical data see Table I.

EXAMPLE 10 A mixture of alkylene oxides consisting of 199 grams (4.53moles) of ethylene oxide and 131.5 grams (2.254 moles) of 1,2-propyleneoxide was reacted with 135 grams (0.68 mole) of phenothiazine at anaverage temperature of about 150 C. and catalyzed with 2 grams of KOH inaccordance with the procedure of Example 3. This represents a molarreactant ratio of alkylene oxides to phenothiazine of 10 to 1, theethylene oxide to 1,2- propylene oxide molar ratio in the mixed alkyleneoxides being approximately 2 to 1. The product was a light brown viscousliquid having an average molecular weight of 601 as calculated from thehydroxyl value. Additional physical data are given in Table I.

EXAMPLE 11 A mixture of alkylene oxides consisting of 94 grams (2.133moles) of ethylene oxide 247.5 grams (4.266 moles) of 1,2-propyleneoxide was reacted to completion with 127 grams (0.64 mole) ofphenothiazine in the presence of 2 grams of KOH catalyst at an averagetemperature of about 140 C. according to the method of Example 3. Basedon the reactants charged, this represents a molar reactant ratio ofalkylene oxides to phenothiazine of 10 to 1, the mole ratio of ethyleneoxide to 1,2-propylene oxide in the mixed oxides being 1 to 2. Thisproduct was a light brown viscous liquid having an average molecularweight as calculated from the hydroxyl value of 616. Other physicalproperties are contained in Table I.

Table I PRODUCTS MADE FROM PHENOTHIAZINE Mole Ratio of Alkylene CloudOxide to Phcnothiazine M01. Hy- Sulfur, Point, Wt. Percent SolubilitiesProduct of Compound M01. Wt., droxyl Con- Specific 10% Ex. No. Wt., fromValue, tent, Np Gravity, aqueous Theory percent percent percent 25/25solu- E. O. P. O. B. O. OH O S tion, water acemethaben- C01, xyn-Hep- 0.tone n01 zene lene tane 431 3. 1.5557 1. IS S S S S S SS 610 2. 79 l.5150 1. 073 IS S S S S S S 461 3. 69 1. 5435 1. 080 IS S S S S S S l,055 1. 615 solid solid 96 S S S S S S IS 601 2. 83 1. 5348 1. 133 26 S SS S S S IS 616 2. 76 1. 5238 1. 103 0 IS S S S S S IS PRODUCTS MADE FROMPHENOTHIAZINE-ti-OXIDE 520 3. 27 4. 75 1.5510 S S S S SS SS IS 635 2. 683. 74 solid S S S S S SS IS 600 2. 84 3. 82 l. 5287 S S S S S S IS S S SS 412 4.13 6. 41 1. 5684 IS IS IS S S S IS 397 4. 29 5. 56 1. 5515 IS SSIS S S S IS 457 3. 72 4. 26 1. 5355 IS S SS S S S IS Legend-11.O.=ethylene oxide; P. O.=propy1ene oxide; B. O.=butylene oxide; S=so1ub1e; SS=slight1y soluble; IS=ins0lub1e. Solubilities determined at25 C. For additional information, see Example 6.

7 EXAMPLE 12 Into a two liter glass flask equipped with a water-cooledreflux condenser and motor-driven stirrer were charged 199 grams (1.0mole) of phenothiazine, 120 grams 1.0 mole) of styrene oxide, and 4grams of solid KOH. Thereupon the contents of the flask were heated to130 C. at which temperature the reaction began to proceed rapidly,raising the temperature of the mixture to about 180 C. After thereaction had progressed for some time at this temperature, more styreneoxide was gradually added under conditions of good mixing until anadditional 480 grams (4.0 moles) had been reacted during a period of 4.5hours. Following the reaction, a portion of the product was neutralizedwith carbon dioxide and filtered to clarify it. This product was a darkreddish brown tacky solid having a theoretical molecular weight of 800.

EXAMPLE 13 A 311 gram portion of the reaction product of Example 12prior to neutralization was charged into a two liter glass flaskequipped with a motor-driven stirrer and a reflux condenser cooled withDry Ice. On heating the contents of the flask to about 180 C., ethyleneoxide was bubbled into the agitated mixture until 512 grams (11.65moles) had been reacted. Following the reaction, the product wasneutralized with carbon dioxide and fil tered. This product was a darkreddish brown viscous liquid having a theoretical molecular weight of2100.

EXAMPLE 14 A 2000 milliliter, electrically heated, steel, rockingtypeautoclave equipped with a thermocouple, pressure gauge, and inlet tubewas charged with 215 grams (1.0 mole) of phenothiazine-S-oxide and 3grams of solid potassium hydroxide. The autoclave was then flushed withdry nitrogen gas, sealed, and placed in an electrically heated steelrocker, set to rocking, and heated slowly to about 100 C. Thereuponliquid ethylene oxide was gradually introduced into the autoclave untila total of 440 grams (10.0 moles) had been added. Throughout theaddition of ethylene oxide the temperature was maintained at about 100to 130 C. and the pressure at about 10 to 50 pounds per square inchgauge. Even after the ethylene oxide had all been added, agitation wascontinued until the reaction was substantially complete, i. e. until thegauge pressure had fallen ofl to about p. s. i. The autoclave was thencooled and the liquid reaction product transferred to a flask. Thisproduct was neutralized with carbon dioxide, heated to 150 C. at apressure of 20 millimeters of mercury absolute to remove low boilingmaterial, and filtered while still hot. The final product was a brownviscous oil which, upon analysis, was found to have a sulfur content of4.75 weight percent and a hydroxyl value, as determined with phthalicanhydride, of 3.27 percent. This product was a mixture ofN-polyoxyethylene derivatives of phenothiazine--oxide having an averagemolecular weight of approximately 520 as calculated from the hydroxylvalue.

Other properties were also determined for the product, viz., therefractive index, specific gravity, cloud point, and solubilities invarious solvents. All of these data are shown in Table I.

The above-described product was tested for fungicidal activity byspraying it in aqueous solution onto the leaves of various vegetableplants and subsequently inoculating the plants with spores ofdisease-producting fungi. At concentrations as low as 1 pound per 100gallons of. water, this product was found to be effective in controllingfungus diseases such as bean mildew and tomato early blight.

EXAMPLE 15 A total of 660 grams (15.0 moles) of ethylene oxide and 215grams (1.0 mole) of phenothiazine-S-oxide were heated at an averagetemperature of about 130 C. in the presence of 3 grams of solidpotassium hydroxide for 8 approximately 5 hours according to theprocedure of Example 1. The final reaction product was a soft, waxysolid, being a mixture of N-polyoxyethylene derivatives ofphenothiazine-S-oxide having an average molecular Weight ofapproximately 635 as calculated from the hydroxyl value. These and otherproperties are given in Table I. This product is similar to the productof the preceding example in fungicidal activity.

EXAMPLE 16 The autoclave employed in the foregoing examples was chargedwith 215 grams (1.0 mole) of phenothiazine-S- oxide, 290 grams (5.0moles) of 1,2-propylene oxide, and 3 grams of solid potassium hydroxide.The contents were then heated for 1.5 hours at a temperature of about150 C. in accordance with the procedure of Example 1. There was obtainedan N-polyoxypropylene-phenothiazine-S-oxide reaction product, i. e. thepolyoxypropylcne chains were attached to the nitrogen atoms of thephenothiazine-S-oxide nuclei. This reaction product in its entirety wasthen heated to about 150 C. and a total of 308 grams (7.0 moles) ofethylene oxide was gradually added, thereby forming polyoxyethyleneextensions of the polyoxypropylene chains. The final product was a darkbrown liquid, having an average molecular weight of approximately 600.This product was found to be an eifective fungicide, being similar inthis respect to the products of Examples 1 and 2. Its properties aregiven in Table I.

EXAMPLE 17 A product similar to that described in the preceding examplewas prepared according to the same procedure. Approximately 215 grams(1.0 mole) of phenothiazine-S- oxide, 290 grams (5.0 moles) of1,2-propylene, and 3 grams of KOH were heated at a temperature of aboutC. until reaction was substantially complete, thereby formingpolyoxypropylene chains on the nitrogen atoms of thephenothiazine-S-oxide nuclei. This reaction product was then maintainedat a temperature of about 130 C. while 629 grams (14.3 moles) ofethylene oxide was gradually added thereto, thereby formingpolyoxyethylene extensions of the polyoxypropylene chains. The finalproduct was a water-soluble amber viscous oil, having a theoreticalmolecular weight of 1113. This product was found to have fungicidalactivity similar to the products of the preceding examples. Theproperties of the product of this example are given in Table I.

EXAMPLE 18 Propylene oxide weighing 290 grams (5.0 moles) was reactedwith 215 grams (1.0 mole) of phenothiazine-S- oxide at an averagetemperature of about C. in the presence of 2 grams of KOH as catalystand according to the procedure employed in the preceding example. Theproduct was a dark brown viscous liquid having an average molecularweight of 412 as calculated from the hydroxyl value. Other product dataare shown in Table I.

EXAMPLE 19 A mixture of 540 grams (7.5 moles) of 1,2- and 2,3- butyleneoxides in a weight ratio of about 9 to 1 was reacted with 323 grams (1.5moles) of phenothiazine-S- oxide at an average temperature of about C.employing 4.5 grams KOH catalyst and in accordance with the procedure ofExample 1. This represents a butylene oxide to phenothiazine-S-oxidemolar ratio of 5 to 1. The product was a dark brown viscous liquidhaving an average molecular weight of 397 as calculated from thehydroxyl value. Product data are shown in Table 1.

EXAMPLE 20 A mixture of alkylene oxides consisting of 264 grams (6.0moles) of ethylene oxide and 348 grams (6.0 moles) of 1,2-propyleneoxide was reacted with 258 grams (1.2 moles) of phenothiazine-S-oxi'deat an average temperature of about 160 C. in the presence of 4 grams ofKOH and in accordance with the procedure of Example 1. This represents amolar ratio of alkylene oxide to phenothiazine-S-oxide of 10 to l, theethylene oxide and 1,2- propylene being present in the mixed alkyleneoxides in an equimolecular proportion. The product was a dark brownviscous liquid having an average molecular weight of 457 as calculatedfrom the hydroxyl value. Additional properties are given in Table I.

The product of Example 7 was tested and found to be an effectiveantitoxidant for lubricating oils, e. g. low viscosity index turbineoil, being superior in this respect to phenothiazine.

EXAMPLE 21 Styrene oxide weighing 300 grams (2.5 moles) was reacted with108 grams (0.5 mole) of phenothiazine-S- oxide in the presence of 2grams of potassium hydroxide and in accordance with the procedure ofExample 3. The reaction was carried out by heating the reactants in arocking-type steel autoclave at a temperature of about 150 C. for fourhours. The N-polyoxyphenylethylenephenothiazine-S-oxide product was adark brown glassy substance having a theoretical molecular weight of815.

We claim:

1. Compounds having the formula the range of 2 to 100.

2. Compounds as defined in claim 1 wherein the alkyl- 10 ene oxide isethylene oxide and n is an integer from 5 to 50.

3. Compounds as defined in claim 1 wherein the alkylene oxide ispropylene oxide and n is an integer from 5 to 50.

4. Compounds as defined in claim 1 wherein the alkylene oxide is abutylene oxide and n is an integer from 5 to 50.

5. Compounds as defined in claim 1 wherein the alkylene oxide is1,2-butylene oxide and n is an integer from 5 to 50.

6. Compounds as defined in claim 1 wherein the alkylene oxide is styreneoxide and n is an integer from 5 to 50.

7. Compounds as defined in claim 1 wherein the alkylene oxide is amixture of alkylene, oxides selected from the group consisting ofethylene, propylene, butylene and styrene oxides.

8. Compounds as defined in claim 7 wherein the mixture of alkyleneoxides is a mixture of ethylene and propylene oxides.

9. Compounds as defined in claim 8 wherein the polyoxyalkylene chain,-(RO),,, has the formula wherein R and R are species of R, one of thembeing the ethylene radical and the other being the 1,2-propylene radicaland x and y are numbers such that x+y=n.

10. Compounds as defined in claim 9 wherein R is the 1,2-propyleneradical and R is the ethylene radical. 11. Compounds as defined in claim2 wherein m is 1. 12. Compounds as defined in claim 3 wherein m is 1.13. Compounds as defined in claim 6 wherein m is 1. 14. Compounds asdefined in claim 10 wherein m is 1.

References Cited in the file of this patent FOREIGN PATENTS 129,843Sweden Oct. 24, 1950

1. COMPOUNDS HAVING THE FORMULA